The present invention includes a carbon/carbon (C/C) composite comprising crystalline silicon carbide which is essentially uniformly distributed on both the internal and external surfaces of the composite, wherein the amount of silicon carbide is in a range of 0.001 to 1.00 weight percent based upon the total weight of the composite, a process for producing said composite and the use of said composite in brake materials for industrial roll goods, automotives, trucks, trains and aircrafts.
The art has recognized the advantages of frictional braking elements, such as brake discs, made of carbon. In more advanced production techniques, the carbon materials are made by molding a mixture of carbon fibers and an organic polymer, and pyrolyzing the polymer binder. The carbon materials have the advantage of a high temperature resistance coupled with a low density, which substantially reduces the dead load making them particularly useful for vehicles such as aircrafts.
Yamazaki et al. (U.S. Pat. No. 5,462,800) teach the formation of a silicon carbide layer in a carbon matrix/carbon fiber composite material by introducing SiO (silicon-mono-oxide) gas at the surface of a C/C composite thereby reacting the SiO with the pyrolytic graphite (and in part the carbon fibers) and forming the silicon carbide layer. According to Yamazaki et al., the silicon carbide is formed to a depth of 3000 xcexcm, and as such, the SiC is essentially present on the external surface of the composite only.
Barnard et al. U.S. Pat. No. 5,665,848, teach a composite comprising carbon containing fibers in a matrix of silicon carbide. An assembly of carbon fibers are impregnated with a organopolysilazane/crosslinker/promoter preceramic mixture to form a xe2x80x9cpre-pregxe2x80x9d. The pre-preg is then exposed to a series of heating steps to form the final ceramic composite. The final ceramic composite contains a matrix of a char which is noncrystalline.
Kaya et al. U.S. Pat. No. 5,459,114 teach a process for producing a ceramic comprising repeating a step of impregnating a metal fiber or ceramic fiber preform with a mixture of organopolysilazane-type polymers. Optionally, the surface of the metal or ceramic fiber containing woven fabric, can be covered with carbon before impregnating with the organopolysilazane. In addition, Kaya et al. teach a step of chemical vapor deposition of a heat resistant ceramic either before or after the organopolysilazane impregnation step. The final composite contains a noncrystalline matrix of the organopolysilazane char.
The large amounts of silicon carbide created in these patents would result in high friction coefficients and high wear rates. None of the above-described patents address the process of coating a porous preform or final body with a small amount (less than 1 wt %) of thin crystalline silicon carbide distributed throughout the part, i.e., on both the internal and external surfaces to reduce the wear rates with either no change or a slight increase in the friction coefficients.
The present inventors have found that small amounts of crystalline silicon carbide uniformly distributed throughout the part results in reduced wear with either no change or a slight increase in the friction coefficient. Also, the properties of this material remain constant during use even after wear of the outer surface.
The present invention includes a C/C composite comprising crystalline silicon carbide which is essentially uniformly distributed on both the internal and external surfaces of the composite, wherein the amount of silicon carbide is in a concentration range of 0.001 to 1.00 weight percent based upon the total weight of the composite, a process for producing said composite and the use of said composite in brake materials for industrial roll goods, automotives, trucks, trains and aircrafts.
Advantages of the present invention will become more apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
The present invention, in part, relates to a C/C composite comprising crystalline silicon carbide which is essentially uniformly distributed on both the internal and external surfaces of the composite, wherein the silicon carbide is in a concentration range of 0.001 to 1.00 weight percent based upon the total weight of the composite. Preferably, the concentration range of the silicon carbide is 0.01 to 0.5 weight percent.
The present invention, in part, relates to a C/C composite containing silicon carbide, wherein the composite has a wear rate in the range of 0.01 to 0.13 inch/s/sxc3x9710xe2x88x924, and a friction coefficient in the range of 0.27 to 0.4. Preferably, the wear rate is in the range of 0.03 to 0.12 inch/s/sxc3x9710xe2x88x924, and the friction coefficient is in the range of 0.28 to 0.395.
The present invention, in part, relates to a C/C composite, wherein the SiC in the composite is at least 60 wt % crystalline, preferably at least 90 wt % crystalline, and most preferably about 100 wt % crystalline.
The present invention, in part, relates to a process for preparing a C/C composite comprising crystalline silicon carbide which is essentially uniformly distributed on both the internal and external surfaces of the composite, said process comprising: contacting a C/C composite preform with a solution of a preceramic compound composed of silicon and carbon; and heating the C/C composite to a temperature sufficient to convert the preceramic compound to silicon carbide; wherein the amount of silicon carbide is in a range of 0.001 to 1.0 weight percent based on the weight of the total composite (in the dried state).
The preceramic compound can be either a polymer or a small molecule and is not specifically limited, but is required to form silicon carbide upon heat treatment. The type of preceramic polymer is not specifically limited, but it is required to have silicon-carbon bonds and the amount of silicon in it should not be so high as to produce an excess of silicon, since excess silicon will attack the carbon fibers. The ratio of silicon to carbon can be controlled by adding a carbon containing crosslinking agent. The type of preceramic small molecule is preferably an alkyl orthosilicate such as tetraethyl orthosilicate (TEOS).
It is preferred that the preceramic polymer composed of silicon and carbon is polycarbosilane, organopolysilazane, polycarbosiloxane, or mixtures thereof.
The organopolysilazanes (or silazane polymers) useful in this invention are generally well known in the art. The organopolysilazanes of this invention generally contain units of the type [R2SiNH], [RSi(NH)1.5] and/or [R3Si(NH)xc2xd] wherein each R is independently selected from the group consisting of hydrogen, alkyl radicals containing 1 to 20 carbon atoms, aryl radicals, and alkenyl radicals. Naturally, the organopolysilazanes useful in this invention may contain other silazane units. Examples of such units include [MeSi(NH)1.5], [Me2SiNH], [ViSi(NH)1.5], [Vi2SiNH], [PhMeSiNH], [PhViSiNH], [MeViSiNH], [HSl(NH)1.5], [H2SiNH], and the like. Mixtures of organopolysilazanes may also be employed in the practice of this invention.
The organopolysilazanes of this invention and their method of preparation can be prepared by techniques well known in the art. Suitable preceramic silazane polymers or organopolysilazanes may be prepared by the methods of Cannady in U.S. Pat. No. 4,540,803 (issued Sep. 10, 1985) and U.S. Pat. No. 4,543,344 (issued Sep. 24, 1985) which are hereby incorporated by reference. Other organopolysilazanes suitable for use in this invention can be prepared by the methods of Gaul in U.S. Pat. No. 4,312,970 (issued Jan. 26, 1982), U.S. Pat. No. 4,340,619 (issued Jul. 20,1982), U.S. Pat. No. 4,395,460 (issued Jul. 26, 1983), and U.S. Pat. No. 4,404,153 (issued Sep. 13, 1983), all of which are hereby incorporated in their entireties by reference. Suitable organopolysilazanes also include those prepare by the methods of Haluska in U.S. Pat. No. 4,482,689 (issued Nov. 13, 1984) and Seyferth et al. in U.S. Pat. No. 4,397,828 (issued Aug. 9, 1983), both of which are hereby incorporated in their entireties by reference. Still other organopolysilazanes include those of Gerdau et al. in European Patent 351,747, those of U.S. Pat. No. 4,543,344, those of European Patent 332,374, those of Lebrun et al. in U.S. Pat. Nos. 4,656,300 and 4,689,252, the disclosures of which are all hereby incorporated in their entireties by reference.
The polycarbosilanes useful in this invention are generally well known in the art. Preferred polycarbosilanes are disclosed in Schilling et al. U.S. Pat. No. 4,414,403, Burns et al. U.S. Pat. No. 4,761,458 and Sartori et al. U.S. Pat. No. 5,087,685, each of which is incorporated by reference in its entirety.
The polycarbosiloxanes useful in this invention are generally well known in the art. Preferred polycarbosiloxanes are disclosed in Yajima et al. U.S. Pat. No. 4,289,720, and Onodera et al. U.S. Pat. No. 6,147,243, each of which is incorporated by reference in its entirety.
The method of crosslinking the preceramic polymer is not particularly limited and depends on the type of polymer. Some polymers can be crosslinked using only heat and optionally a crosslinking promoter (curing agent). For example, a polymer such as poly(methyl-vinyl)silazane can be crosslinked using dicumyl peroxide as the crosslinking promoter.
Crosslinking promoters which are useful in the present invention are well known in the art. Examples include organic peroxides such as dibenzoyl peroxide, bis-p-chlorobenzoyl peroxide, bis-2,-dichlorobenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl perbenzoate, 2,5-bis(t-butylperoxy)-2,3-dimethylhexane and t-butyl peracetate.
The crosslinking promoter is present in an effective amount, i.e. an amount sufficient to induce crosslinking in the polymer. Therefore, the actual amount of the crosslinking promoter will depend on the activity of the promoter used and the amount of polymer present. Normally however, the peroxide curing promoter will be present at about 0.1 to 5.0 weight percent based on the weight of the compound to be cured with the preferred amount being about 2.0 weight percent.
The solvent may include any which acts as a solvent for the preceramic polymer, and if present, the crosslinking agent and promoter and which do not cause rearrangement of these species. Examples of such solvents include alkanes such as pentane, hexane, octane etc.; halogenated alkanes such as methylene chloride, chloroform, methylene bromide, etc.; ethers such as tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene, xylene etc.; alcohols such as methanol, ethanol, ethylene glycol, etc.; and ketones such as acetone, methyl ethyl ketone, etc. The concentration of the preceramic polymer in the solution is preferably 0.05-10 wt %. More preferably, the preceramic polymer in the solution is 0.1-5 wt %.
The present invention, in part, relates to a process for preparing a C/C composite comprising a layer of essentially uniformly distributed silicon carbide, wherein said C/C composite has a 0.005 to 1.0 percent weight gain after solvent removal. Preferably the C/C composite has a 0.01 to 0.3 percent weight gain after solvent removal.
The preceramic polymers will have different curing (crosslinking) mechanisms, depending upon their structure. Most preferred is the use of poly(methylvinyl)silazane which crosslinks via a free radical mechanism acting on the vinyl groups. The free radical is generated by the decomposition of an organic peroxide, such as dicumyl peroxide.
The temperature of the crosslinking step varies depending upon the type of preceramic polymer and the crosslinking promoter that are used. Preferably, the temperature is in the range of 50 to 200xc2x0 C.
The pyrolysis step, wherein the preceramic polymer is converted to silicon carbide, is performed by heating the part to at least 1500xc2x0 C., preferably the part is heated to 1600xc2x0 C. If the part contains reactive carbon, then the pyrolysis step is performed in an inert atmosphere, such as argon or nitrogen.
The present invention, in part, relates to a process for preparing a C/C composite comprising a layer of essentially uniformly distributed silicon carbide, wherein the density of the C/C composite effectively remains constant even after the silicon carbide has been added.
The term xe2x80x9cpreformxe2x80x9d as used herein, is defined as a carbon composite prepared by combining carbon fibers with an organic polymer, pyrolizing the mixture, and optionally densifying the composite by depositing carbon through chemical vapor deposition (CVD or CVI). This preform is a porous material having open voids. The amount of void space can be reduced by: (1) adding further organic polymer and pyrolizing the mixture; (2) further chemical vapor deposition of carbon; or (3) repeating steps (1) and/or (2) at least one time.
The preceramic polymers can be added to the C/C composite at the preform stage or can be added after the void space of the C/C composite has been reduced by any of steps (1) to (3) as described in the previous paragraph. It should be noted that when the preceramic polymer is added after any of steps (1) to (3), the C/C composite contains active carbon. The presence of active carbon requires that the pyrolysis step of the preceramic polymer is performed in an inert atmosphere (such as argon or nitrogen) in order to prevent the formation of carbon oxides due to the reaction between oxygen and the active carbon.
When the preceramic polymers are added to the C/C composite at the preform stage a crosslinking agent is used to increase the concentration of carbon in the composite and to reduce the likelihood that reactive silicon atoms on the preceramic polymer will react directly with the fibers of the composite. The crosslinking agent and the preceramic polymer may be blended in nearly any ratio desired to provide sufficient flow and final cure. Generally, however, the crosslinking agent is present in an amount of at least about 0.01 wt % crosslinking agent based on the weight of the preceramic polymer with a range of about 0.01 to about 50 wt % being preferred. The type of crosslinking agent can be any compound that reacts with the preceramic polymer. It is preferred to use a diisocyanate such as 1,6-diisocyanatohexane.
When the preceramic compound is an alkyl orthosilicate, the process of forming the silicon carbide on the inner and outer surfaces of the composite is different in some respects from the process using a preceramic polymer due to the nature of the alkyl orthosilicate. The alkyl orthosilicate is first dissolved in a solvent, which is typically an alcohol solvent such as ethanol. Then a concentrated strong acid (such as HCl, HCIO4, H2SO4, perfluoroacetic acid, phosphoric acid, etc.) is added to begin the precipitation reaction. Since the precipitation reaction begins before the solution is added to the preform, the timing of the initiation of the precipitation is important. If the precipitation reaction is allowed to proceed too long before adding to the preform, the precipitate particles will become too large to enter the small pores of the preform. Thus, it is preferred to begin the precipitation reaction immediately prior to infiltrating the solution into the preform. Once the solution is added to the preform, the preform is allowed to sit in the solution until the precipitation reaction is essentially complete, typically 24 hours. The infiltrated part is removed from the solution and the solvent is removed. Then the silicon carbide is formed in a pyrolysis step which is optionally coincidental with the step of subjecting the part to carbon CVD to increase the density.
An aspect of this invention is that the silicon carbide is formed on both the internal and external surfaces of the C/C composite. This is advantageous when the friction, resulting from the use of this material in brakes, begins to wear the surface of the composite material. By having the silicon carbide not merely on the outer surface, the overall mechanical properties do not decrease, e.g., the wear rates remain essentially constant even when the outer surface of the brake has been worn away.